WO2019132023A1 - Dispersion aqueuse de pigment - Google Patents

Dispersion aqueuse de pigment Download PDF

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Publication number
WO2019132023A1
WO2019132023A1 PCT/JP2018/048535 JP2018048535W WO2019132023A1 WO 2019132023 A1 WO2019132023 A1 WO 2019132023A1 JP 2018048535 W JP2018048535 W JP 2018048535W WO 2019132023 A1 WO2019132023 A1 WO 2019132023A1
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WO
WIPO (PCT)
Prior art keywords
pigment
meth
less
water
acrylic resin
Prior art date
Application number
PCT/JP2018/048535
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English (en)
Japanese (ja)
Inventor
太生 川口
Original Assignee
花王株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201880082951.4A priority Critical patent/CN111511850A/zh
Priority to US16/957,547 priority patent/US20210062030A1/en
Priority to EP18896153.6A priority patent/EP3733795A4/fr
Publication of WO2019132023A1 publication Critical patent/WO2019132023A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/005—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant

Definitions

  • the present invention relates to an aqueous pigment dispersion, an aqueous ink containing the aqueous pigment dispersion, and a method for producing the aqueous pigment dispersion.
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • PE polyethylene
  • PP polypropylene
  • NY nylon
  • printing has been performed on a resin printing medium of the above by using a solvent-based ink, a UV curing ink, or the like.
  • utilization of an inkjet recording method, a flexographic printing method, and a gravure printing method is required as a printing method using an aqueous ink.
  • JP-A-2004-131586 aims to obtain a water-based pigment dispersion or the like excellent in storage stability, by obtaining a colored film having both light resistance and abrasion resistance.
  • an aqueous pigment dispersion containing a pigment, a (meth) acrylic ester resin and a polyurethane resin the (meth) acrylic ester resin is contained more as a resin component as a resin component, and the polyurethane resin is in a specific range
  • An aqueous pigment dispersion or the like having an average dispersed particle size of JP-A-2013-53200 discloses a pigment aqueous dispersion composition exhibiting excellent dispersibility and the like, and an aqueous film exhibiting excellent gloss while exhibiting excellent image density etc.
  • a pigment aqueous dispersion composition containing a specific aqueous polyurethane dispersion resin, a pigment and a dispersant is disclosed.
  • JP-A-2005-48016 Patent Document 3 discloses a pigment, an aqueous medium, and a hydrophobic property for the purpose of providing a pigment dispersion and the like having excellent glossiness and storage stability of the ink composition.
  • Solid weight ratio of the added amount of the crosslinking agent (the amount of the crosslinking agent / (hydrophobic monomer and hydrophilic monomer), containing at least a copolymer resin of a hydrophilic monomer and a hydrophilic monomer, a urethane resin, and a crosslinking agent
  • the pigment dispersion liquid etc. which are the specific range with the total amount of the copolymer resin of these, and a urethane resin are disclosed.
  • WO 2009/066577 (patent document 4) prepares an aqueous pigment ink for ink jet recording, which is excellent in abrasion resistance, and can provide a colored image excellent in color development on plain paper and gloss on exclusive paper.
  • Carbon black or organic pigment (meth) acrylic copolymer, specific polyoxyethylene / polyoxypropylene block copolymer, polyether polyurethane, base for the purpose of providing an aqueous pigment dispersion that can be And water-containing aqueous pigment dispersions are disclosed.
  • the present invention is an aqueous pigment dispersion in which a pigment is dispersed in an aqueous medium with a polymer dispersant,
  • the polymer dispersant contains a (meth) acrylic resin (A) having an acid group and a polyurethane resin (B),
  • the (meth) acrylic resin (A) is crosslinked by the crosslinking agent (C), and the degree of crosslinking of the (meth) acrylic resin (A) [the molar equivalent number of the crosslinkable functional group of the crosslinking agent (C)
  • the number of molar equivalents of acid groups of (meth) acrylic resin (A) is 0.12 or more and 0.65 or less
  • the present invention relates to an aqueous pigment dispersion in which the mass ratio of the pigment in the total solid content of the aqueous pigment dispersion [pigment / (total solid content of the aqueous pigment dispersion)] is 0.25 or more and 0.75 or less.
  • a method of blending a polymer emulsion as a fixing agent in the ink is known as a method of improving the adhesion.
  • a water-based ink having a high content of polymer emulsion is used for a non-water absorbing print medium, the storage stability of the ink and the print density tend to be reduced.
  • Patent Document 1 although the adhesion to the non-water absorbing print medium is improved to some extent, a high print density can not be secured.
  • Patent Document 2 although the print density when printed on plain paper is improved, both the adhesion to the non-water absorbent print medium and the print density can not be satisfied.
  • the present invention is an aqueous pigment dispersion having a high printing density while maintaining excellent adhesion to a non-water absorbing print medium by using the aqueous ink excellent in storage stability, and production of the aqueous pigment dispersion. On the way.
  • the adhesion between the pigment particles or between the pigment particles and the printing medium can be strengthened.
  • storage stability decreases, and after the ink droplets contact the printing medium, phase separation occurs between the pigment dispersant and the polymer of the emulsion, which results in local aggregation of pigment particles.
  • the smoothness of the coated film surface is reduced, which is considered to be a cause of the reduction in printing density. Therefore, the present inventor can maintain excellent storage stability, while pigment particles do not aggregate locally in an environment where the ink vehicle is dried on the surface of the printing medium as during printing. We aimed to obtain the performance that can firmly maintain the adhesion between the paper and the printing medium.
  • the present inventor contains a pigment of two different resins, and disperses the pigment with a polymer dispersant in which at least one of the resins is crosslinked, and the content of the pigment falls within a specific range. It has been found that the storage stability is excellent, and by using for a water-based ink, both the adhesion to a non-water absorbing print medium and the print density can be improved.
  • an aqueous pigment dispersion in which a pigment is dispersed in an aqueous medium with a polymer dispersant,
  • the polymer dispersant contains a (meth) acrylic resin (A) having an acid group and a polyurethane resin (B),
  • the (meth) acrylic resin (A) is crosslinked by the crosslinking agent (C), and the degree of crosslinking of the (meth) acrylic resin (A) [the molar equivalent number of the crosslinkable functional group of the crosslinking agent (C)
  • the number of molar equivalents of acid groups of (meth) acrylic resin (A) is 0.12 or more and 0.65 or less
  • An aqueous pigment dispersion, wherein the mass ratio of the pigment in the total solid content of the aqueous pigment dispersion [pigment / (total solid content of the aqueous pigment dispersion)] is 0.25 or more and 0.75 or less.
  • a method for producing an aqueous pigment dispersion which comprises the following steps 1 and 2.
  • Step 1 Step of dispersing a pigment mixture containing a pigment, a (meth) acrylic resin (A) having an acid group, and a polyurethane resin (B) to obtain a dispersion
  • Step 2 obtained in Step 1 Step [3] of Crosslinking the Dispersion with a Crosslinking Agent (C)
  • Step 3 Step [3] of Crosslinking the Dispersion with a Crosslinking Agent (C)
  • a water based ink comprising the water based pigment dispersion as described in the above [1].
  • [4] Use of the water-based ink according to [3] for inkjet printing.
  • an aqueous pigment dispersion having a high printing density while maintaining excellent adhesion to a non-water absorbing print medium by using the aqueous ink excellent in storage stability the aqueous pigment dispersion It is possible to provide an aqueous ink containing the same and a method for producing the aqueous pigment dispersion.
  • the aqueous pigment dispersion of the present invention is an aqueous pigment dispersion in which a pigment is dispersed in an aqueous medium with a polymer dispersant, and the polymer dispersant comprises an (meth) acrylic resin (A) having an acid group, A polyurethane resin (B) is contained, the (meth) acrylic resin (A) is crosslinked by a crosslinking agent (C), and the degree of crosslinking of the (meth) acrylic resin (A) [crosslinking agent (C)
  • the molar equivalent number of the crosslinkable functional group of (a) / the molar equivalent number of the acid group of the (meth) acrylic resin (A)] is 0.12 or more and 0.65 or less in the total solid content of the aqueous pigment dispersion
  • the mass ratio of the pigment of [pigment / (total solid content of the aqueous pigment dispersion)] is 0.25 or more and 0.75 or less.
  • the "aqueous medium” means a medium in which water occupies the largest proportion in the medium in which the pigment is dispersed.
  • the aqueous pigment dispersion of the present invention is excellent in storage stability and can obtain good printed matter having excellent adhesion and high printing density, and therefore, for flexographic printing ink, gravure printing ink, or inkjet ink It can be suitably used as an aqueous pigment dispersion of the above, and in particular, it is preferable to use as an aqueous pigment dispersion for inkjet ink.
  • the aqueous pigment dispersion of the present invention is excellent in storage stability, and when used in an aqueous ink, it can improve both the adhesion to a non-water absorbing print medium and the print density. Although the reason is not clear, it is considered as follows. In the water-based pigment dispersion of the present invention, it is presumed that the pigment is dispersed in the water-based medium in a state where the polymer dispersant is adsorbed or immobilized on the pigment surface.
  • the polymer dispersant contains a (meth) acrylic resin having an acid group and a polyurethane resin, and the (meth) acrylic resin is crosslinked by a crosslinking agent, and the degree of crosslinking of the (meth) acrylic resin Is within the specific range, the (meth) acrylic resin is adsorbed or immobilized on the pigment surface together with the polyurethane resin, and the pigment is stably dispersed, and the polyurethane resin improves the adhesion to the non-water absorbing print medium.
  • the mass ratio of the pigment in the total solid content of the aqueous pigment dispersion is within a specific range, and the pigment is dispersed with a polymer dispersant containing a (meth) acrylic resin and a polyurethane resin, and the pigment surface is divided into two types. Since it is adsorbed or immobilized, it is difficult to cause phase separation of the resin at the time of coating film formation and drying of the ink vehicle, resulting in a coating film having a smooth surface, and it is presumed that the printing density is improved.
  • the pigment used in the present invention may be either an inorganic pigment or an organic pigment, and lake pigments and fluorescent pigments can also be used. In addition, if necessary, they may be used in combination with an extender pigment.
  • the inorganic pigment include carbon black, titanium oxide, iron oxide, iron oxide, metal oxides such as iron oxide and chromium oxide, and pearlescent pigments. Particularly in the case of black ink, carbon black is preferred. As carbon black, furnace black, thermal lamp black, acetylene black, channel black etc. are mentioned.
  • organic pigment examples include azo pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments and chelate azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, iso indo dyes
  • azo pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments and chelate azo pigments
  • phthalocyanine pigments perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments
  • iso indo dyes Polycyclic pigments such as linone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, and Sureren pigments, and the like can be mentioned.
  • the hue is not particularly limited, and achromatic pigments such as white, black and gray; and chromatic pigments such as yellow, magenta, cyan, blue, red, orange and green may be used.
  • achromatic pigments such as white, black and gray
  • chromatic pigments such as yellow, magenta, cyan, blue, red, orange and green
  • the extender pigment include silica, calcium carbonate, talc and the like.
  • the said pigment can be used individually or in mixture of 2 or more types.
  • the pigment is a pigment dispersed in a water-based pigment dispersion, a polymer dispersant, or a pigment-containing polymer dispersant, that is, a pigment-containing polymer particle (hereinafter simply referred to as "pigment-containing polymer particle") Also referred to as The pigment is preferably contained as a pigment-containing polymer particle from the viewpoint of storage stability of the aqueous pigment dispersion, adhesion and print density.
  • the polymer dispersant used in the present invention contains a (meth) acrylic resin (A) and a polyurethane resin (B).
  • the mass ratio of the polyurethane resin (B) to the (meth) acrylic resin (A) in the aqueous pigment dispersion [polyurethane resin (B) / (meth) acrylic resin (A)] is preferably at least 0.15, More preferably 0.5 or more, still more preferably 1 or more, still more preferably 1.5 or more, still more preferably 2 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 7 or less More preferably, it is 5 or less.
  • the form of presence of the polymer dispersant in the aqueous pigment dispersion is the form in which the polymer dispersant is adsorbed to the pigment, the pigment inclusion (capsule) form in which the polymer dispersant contains the pigment, and the polymer dispersant in the pigment There is a form that is not adsorbed.
  • the form in which the pigment is contained by the polymer dispersant that is, the form of pigment-containing polymer particles is preferable, and the pigment-encapsulated state in which the pigment is contained by the polymer dispersant is more preferable.
  • the (meth) acrylic resin (A) used in the present invention has an acid group from the viewpoint of dispersion stability of the pigment, and at least a part of the acid group is neutralized with a neutralizing agent. Is preferred. As a result, charge repulsion developed after neutralization is increased, aggregation of pigment particles in the aqueous pigment dispersion can be suppressed, thickening can be suppressed, and storage stability is considered to be improved.
  • acid groups are released by dissociation of a carboxy group (-COOM 1 ), a sulfonic acid group (-SO 3 M 1 ), a phosphoric acid group (-OPO 3 M 1 2 ), etc. and hydrogen ions are released.
  • M 1 represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium.
  • a carboxy group (-COOM 1 ) is preferable from the viewpoint of storage stability of the aqueous pigment dispersion, adhesion and print density.
  • the acid value of the (meth) acrylic resin (A) is preferably 50 mg KOH / g or more, more preferably 70 mg KOH / g or more, and preferably 300 mg KOH / g or less, more preferably 270 mg KOH / g or less, more preferably Is 250 mg KOH / g or less. If the acid value is in the above range, the amount of the acid group and its neutralized acid group is sufficient, and the dispersion stability of the pigment is secured. It is also preferable from the viewpoint of the balance between the affinity of the polymer dispersant and the aqueous medium and the interaction between the polymer dispersant and the pigment.
  • the acid value of the (meth) acrylic resin (A) can be calculated from the mass ratio of the constituting monomers. It can also be determined by a method of dissolving or swelling (meth) acrylic resin (A) in a suitable organic solvent (for example, methyl ethyl ketone (MEK)) and performing titration.
  • a suitable organic solvent for example, methyl ethyl ketone (MEK)
  • the (meth) acrylic resin (A) used in the present invention comprises (a-1) a carboxy group-containing monomer (hereinafter also referred to as "component (a-1)”) and (a-2) a hydrophobic monomer (
  • component (a-1) a carboxy group-containing monomer
  • component (a-2) a hydrophobic monomer
  • a vinyl-based polymer obtained by copolymerizing a monomer mixture A hereinafter, also simply referred to as “monomer mixture A”
  • the vinyl polymer has a constituent unit derived from the component (a-1) and a constituent unit derived from the component (a-2).
  • the vinyl polymer further comprises a constituent unit derived from (a-3) a macromonomer (hereinafter also referred to as “(a-3) component”) and / or (a-4) a nonionic monomer (hereinafter "(a-) 4)
  • a component unit derived from “also referred to as component” may be contained.
  • the (a-1) carboxy group-containing monomer is preferably used as a monomer component of the (meth) acrylic resin (A) from the viewpoint of improving the dispersion stability of the pigment.
  • a carboxylic acid monomer is used as the carboxy group-containing monomer (a-1).
  • the carboxylic acid monomer include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, 2-methacryloyloxymethylsuccinic acid and the like, with preference given to (meth) acrylic acid.
  • “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.
  • hydrophobic monomer is used as a monomer component of the (meth) acrylic resin (A) from the viewpoint of improving the adsorptivity of the polymer dispersant to the pigment and improving the dispersion stability of the pigment.
  • hydrophobic means that when the monomer is dissolved in 100 g of ion-exchanged water at 25 ° C. until saturation, the amount of dissolution is less than 10 g.
  • the amount of the hydrophobic monomer (a-2) dissolved is preferably 5 g or less, more preferably 1 g or less, from the viewpoint of the adsorptivity of the polymer dispersant to the pigment.
  • the hydrophobic monomer is preferably at least one selected from (meth) acrylates having an aliphatic alcohol-derived hydrocarbon group and aromatic group-containing monomers.
  • (meth) acrylate is at least one selected from acrylate and methacrylate.
  • the (meth) acrylate having a hydrocarbon group derived from an aliphatic alcohol is preferably one having a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms.
  • (Meth) acrylates having a linear alkyl group such as stearyl (meth) acrylate; isopropyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isopentyl (meth) acrylate, isooctyl (meth) acrylate, Having branched
  • the aromatic group-containing monomer is preferably a vinyl monomer having an aromatic group having 6 to 22 carbon atoms, which may have a substituent containing a hetero atom, and a styrenic monomer, aromatic group-containing (meth) Acrylate is more preferred.
  • the molecular weight of the aromatic group-containing monomer is preferably less than 500.
  • styrene-based monomer styrene, ⁇ -methylstyrene, 2-methylstyrene, vinyl toluene and divinylbenzene are preferable, and styrene and ⁇ -methylstyrene are more preferable.
  • aromatic group containing (meth) acrylate phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are preferable, and benzyl (meth) acrylate is more preferable.
  • hydrophobic monomer (a-2) two or more of the above-mentioned monomers may be used, and a styrenic monomer and an aromatic group-containing (meth) acrylate may be used in combination.
  • the macromonomer is a compound having a number average molecular weight of 500 to 100,000 having a polymerizable functional group at one end, and from the viewpoint of improving the dispersion stability of the pigment, a (meth) acrylic resin ( It can be used as a monomer component of A).
  • the polymerizable functional group present at one end is preferably an acryloyloxy group or a methacryloyloxy group, and more preferably a methacryloyloxy group.
  • the number average molecular weight of the (a-3) macromonomer is preferably 1,000 or more and 10,000 or less.
  • the (a-3) macromonomer is preferably an aromatic group-containing monomer type macromonomer and a silicone type macromonomer, and more preferably an aromatic group containing monomer type macromonomer.
  • the aromatic group-containing monomer constituting the aromatic group-containing monomer macromonomer include the aromatic group-containing monomers described in the (a-2) hydrophobic monomer, and styrene and benzyl (meth) acrylate are preferable, Styrene is more preferred.
  • styrenic macromonomers include AS-6 (S), AN-6 (S), HS-6 (S) (trade names of Toagosei Co., Ltd.), and the like.
  • silicone macromonomers include organopolysiloxanes having a polymerizable functional group at one end.
  • the nonionic monomer (a-4) can be used as a monomer component of the (meth) acrylic resin (A) from the viewpoint of the dispersion stability of the pigment.
  • Specific examples of the commercially available component (a-4) include NK esters M-20G, 40G, 90G, 230G, etc. of Shin-Nakamura Chemical Co., Ltd., and Blemmer PE-90 of NOF Corporation. 200, 350, etc., PME-100, 200, 400, etc. PP-500, 800, 1000, etc. AP-150, 400, 550, etc., 50 PEP-300, 50 POEP-800 B, 43 PAPE And -600 B and the like.
  • the (meth) acrylic resin (A) used in the present invention is a structural unit derived from at least one (a-1) carboxy group-containing monomer selected from acrylic acid and methacrylic acid, and an aliphatic alcohol It is preferable that it is a vinyl polymer containing structural units derived from at least one (a-2) hydrophobic monomer selected from (meth) acrylates having a hydrocarbon group derived from the above and aromatic group-containing monomers, It may be a vinyl-based polymer containing (a-3) a structural unit derived from a macromonomer, and (a-4) a structural unit derived from a nonionic monomer.
  • the content of the constituent units derived from the components (a-1) and (a-2) in the acrylic resin (A) is as follows from the viewpoint of improving the dispersion stability of the pigment.
  • the content of the component (a-1) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 75% by mass or less, more preferably 60% by mass.
  • the content of the component (a-2) is preferably 25% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass. % Or less, more preferably 75% by mass or less.
  • the (a-1) to (a-4) components at the time of producing the (meth) acrylic resin (A) when the structural unit derived from the (a-3) and / or the (a-4) component is contained The content in the monomer mixture A or the content of the constituent units derived from the components (a-1) to (a-4) in the (meth) acrylic resin (A) improves the dispersion stability of the pigment. From the point of view, it is as follows.
  • the content of the component (a-1) is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 30% by mass or less, more preferably 28% by mass. % Or less, more preferably 25% by mass or less.
  • the content of the component (a-2) is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 65% by mass or less, more preferably 60% by mass % Or less, more preferably 55% by mass or less.
  • the content of the component (a-3) is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and preferably Is 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.
  • the content of the component (a-4) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably Is 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.
  • the mass ratio of [(a-1) component / (a-2) component] is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.25 or more, and preferably 3 More preferably, it is 2 or less, more preferably, 1 or less, and still more preferably 0.5 or less.
  • the mass ratio of [(a-1) component / [(a-2) component + (a-3) component]] is preferably 0.03 or more, and more preferably It is preferably 0.05 or more, more preferably 0.1 or more, and preferably 1 or less, more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.5 or less. .
  • the (meth) acrylic resin (A) is produced by copolymerizing the monomer mixture A by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. Among these polymerization methods, the solution polymerization method is preferred.
  • the solvent used in the solution polymerization method is not particularly limited, but a polar organic solvent is preferred. When the polar organic solvent is miscible with water, it can also be used by mixing with water. Examples of the polar organic solvent include aliphatic alcohols having 1 to 3 carbon atoms, ketones having 3 to 5 carbon atoms, ethers, and esters such as ethyl acetate.
  • a polymerization initiator and a polymerization chain transfer agent can be used.
  • a polymerization initiator such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), t-butyl peroxy octoate, benzoyl peroxide, etc.
  • Known radical polymerization initiators such as organic peroxides of the above can be used.
  • the amount of the radical polymerization initiator is preferably 0.001 to 5 moles, more preferably 0.01 to 2 moles per mole of the monomer mixture A.
  • the polymerization chain transfer agent known chain transfer agents such as mercaptans such as octyl mercaptan and 2-mercaptoethanol, and thiuram disulfides can be used.
  • mercaptans such as octyl mercaptan and 2-mercaptoethanol
  • thiuram disulfides can be used.
  • mode of chain of the polymerization monomers there is no limitation on the mode of chain of the polymerization monomers, and any polymerization mode such as random, block, graft and the like may be used.
  • the preferred polymerization conditions vary depending on the type of polymerization initiator, monomer, solvent, etc., but usually the polymerization temperature is preferably 30 ° C. or more, more preferably 50 ° C. or more, and preferably 95 ° C. or less. More preferably, it is 80 ° C. or less.
  • the polymerization time is preferably 1 hour or more, more preferably 2 hours or more, and preferably 20 hours or less, more preferably 10 hours or less.
  • the polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
  • the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation, solvent evaporation and the like. In addition, the obtained polymer can be purified by removing unreacted monomers and the like by reprecipitation, membrane separation, chromatography, extraction and the like.
  • the number average molecular weight of the (meth) acrylic resin (A) used in the present invention is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 8,000 or more, and preferably 100 Or less, more preferably 80,000 or less, still more preferably 60,000 or less.
  • the number average molecular weight of the (meth) acrylic resin (A) is in the above-mentioned range, the adsorptivity to the pigment is sufficient, and dispersion stability can be exhibited.
  • the measurement of a number average molecular weight can be performed by the method as described in an Example.
  • Polyurethane resin (B) The polyurethane resin (B) used in the present invention is obtained by the polyaddition reaction of an organic compound (polyol) having two or more alcoholic hydroxyl groups in one molecule and a polyisocyanate.
  • the polyol is not particularly limited as long as it is a compound having two or more alcoholic hydroxyl groups in one molecule, and polycarbonate polyol, polyester polyol, polyether polyol is preferable, and polycarbonate polyol, polyester polyol is more preferable. That is, the polyurethane resin (B) is preferably a polycarbonate-based polyurethane or a polyester-based polyurethane.
  • the polycarbonate polyol can be obtained by reacting a carbonate compound and a diol.
  • the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and diethylene carbonate.
  • the diol include aliphatic diols which may be substituted by lower alcohols; alicyclic diols such as cyclohexanediol and hydrogenated xylylene glycol; and aromatic diols such as xylylene glycol.
  • aliphatic diols are preferable, and carbon chains such as 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, heptanediol, octanediol, nonanediol and the like have a length of 4
  • the aliphatic diol of 9 or more is more preferable.
  • Polyester polyols can be obtained by condensation of low molecular weight diols with dicarboxylic acids.
  • low molecular weight diols include diols having 2 to 6 carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and 1,4-butanediol. Among these, ethylene glycol, propylene glycol, 1,4-butanediol and the like are preferable.
  • dicarboxylic acids examples include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and brassic acid; and aromatic dibasic acids such as isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid Basic acids may be mentioned.
  • aliphatic dibasic acids are preferable, and dibasic acids having a methylene chain length of 4 to 8 such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like are more preferable.
  • polyether polyols As polyether polyols, cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin etc. are used alone or in combination of compounds having active hydrogen atoms as a catalyst, etc.
  • the polymer obtained by mixing and carrying out ring-opening polymerization etc. is mentioned.
  • polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned.
  • polyisocyanate examples include linear aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane 4, Aliphatic diisocyanates having a cyclic structure such as 4'-diisocyanate; Aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate and tetramethyl xylylene diisocyanate; Aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; Modified products (carbodiimide, uretdione, modified products containing uretimine, etc.) Be Among these, aliphatic diisocyanates such
  • the polyurethane resin (B) preferably has an acid group from the viewpoint of dispersion stability in an aqueous medium, storage stability of an aqueous pigment dispersion, and adhesion and print density.
  • the (meth) acrylic resin (A) and the polyurethane resin (B) are crosslinked by the crosslinking agent (C), and the respective acids of the acrylic resin (A) and the polyurethane resin (B)
  • part of the groups be crosslinked by the crosslinking agent (C).
  • at least a part of the acid groups is preferably neutralized with a neutralizing agent.
  • the neutralizing agent examples include alkylamines such as butylamine and triethylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and inorganic bases such as morpholine, ammonia and sodium hydroxide.
  • a polyurethane resin (B) As an acid group of a polyurethane resin (B), the thing similar to what was mentioned by the (meth) acrylic-type resin (A) is mentioned. Among them, preferred is a carboxy group (-COOM 1 ) from the viewpoint of the storage stability of the water-based pigment dispersion, the adhesion and the printing density.
  • the polyurethane resin (B) having a carboxy group can be obtained by polyaddition reaction of a polyol, a polyisocyanate and a dialkanolcarboxylic acid. Examples of the dialkanol carboxylic acid include dimethylol butanoic acid, dimethylol propionic acid and salts thereof.
  • the reaction solvent for the polyaddition reaction includes acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, toluene, xylene and the like.
  • a chain extender and a reaction terminator may be used in combination, as necessary.
  • the molecular weight can be further increased by using a chain extender.
  • the chain extender includes polyols and polyamines, and the reaction terminator includes monoalcohols and monoamines.
  • the polyurethane resin (B) is preferably used as an emulsion, and the emulsion may optionally contain a dispersant such as a surfactant.
  • the acid value of the polyurethane resin (B) is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g or more, still more preferably 20 mg KOH / g or more, and preferably 50 mg KOH or more, from the viewpoint of adhesion to the printing medium. / G or less, more preferably 40 mg KOH / g or less, still more preferably 35 mg KOH / g or less.
  • ⁇ Crosslinking agent (C)> at least the (meth) acrylic resin is crosslinked by the crosslinking agent (C) from the viewpoint of storage stability of the aqueous pigment dispersion, adhesion and print density.
  • the crosslinking agent (C) used in the present invention is efficiently reacted with the acid group of the (meth) acrylic resin (A) in a medium composed mainly of water, storage stability of the aqueous pigment dispersion, and adhesion
  • the water solubility (mass ratio) of the crosslinking agent (C) is preferably 50% or less, more preferably 40% or less, and still more preferably 35% or less from the viewpoint of the properties and the printing density.
  • the water solubility rate% (mass ratio) refers to the dissolution rate (%) when 10 parts by mass of the crosslinking agent (C) is dissolved in 90 parts by mass of water at room temperature of 25 ° C.
  • the crosslinking agent (C) is preferably a compound having two or more epoxy groups in a molecule, more preferably a compound having a glycidyl ether group, and still more preferably a polyhydric alcohol having a hydrocarbon group having 3 to 8 carbon atoms.
  • Polyglycidyl ether compounds of The molecular weight of the crosslinking agent (C) is preferably 120 or more, more preferably 150 or more, still more preferably 200 or more, and preferably 2000 or less from the viewpoint of reaction ease and storage stability of the aqueous pigment dispersion. More preferably, it is 1500 or less, More preferably, it is 1000 or less.
  • the epoxy equivalent of the crosslinking agent (C) is preferably 90 or more, more preferably 100 or more, still more preferably 110 or more, and preferably 300 or less, more preferably 200 or less, still more preferably 150 or less.
  • the number of epoxy groups of the crosslinking agent (C) is 2 or more per molecule, and preferably 6 or less per molecule, from the viewpoint of efficiently reacting with the acid group to improve the storage stability of the aqueous pigment dispersion. And, from the viewpoint of market availability, more preferably 4 or less.
  • crosslinking agent (C) examples include polypropylene glycol diglycidyl ether (water solubility 31%), glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether (water solubility 27%), sorbitol polyglycidyl Ethers, pentaerythritol polyglycidyl ether (water solubility 0%), resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyglycidyl ethers such as hydrogenated bisphenol A type diglycidyl ether, etc. Can be mentioned. Among these, one or more selected from trimethylolpropane polyglycidyl ether and pentaerythritol polyglycidyl ether are preferable.
  • a part of the acid groups of the (meth) acrylic resin (A) is neutralized by the neutralizing agent described later, and a part of the acid groups of the (meth) acrylic resin (A)
  • a water-based pigment dispersion in which a pigment is dispersed in an aqueous medium by a crosslinked polymer dispersant (hereinafter, also referred to as “crosslinked polymer dispersant”) by having a crosslinked structure in which the pigment is crosslinked by a crosslinking agent (C) Is preferred.
  • the degree of crosslinking is the storage stability of the aqueous pigment dispersion, and the adhesion and From the viewpoint of printing density, it is 0.12 or more, preferably 0.16 or more, more preferably 0.2 or more, and 0.65 or less, preferably 0.6 or less, more preferably 0. Or less, more preferably 0.4 or less, and still more preferably 0.3 or less.
  • the degree of crosslinking in the present invention is an apparent degree of crosslinking calculated from the acid value of the (meth) acrylic resin (A) and the equivalent of the crosslinkable functional group of the crosslinking agent (C).
  • the polyurethane resin (B) has an acid group
  • a crosslinked structure is formed between the acid group of the polyurethane resin (B) and the crosslinking agent (C)
  • the crosslinking degree of the polymer dispersant From the viewpoint of controlling the storage stability of the aqueous pigment dispersion and improving the adhesion and the printing density, the crosslinkability of the crosslinking agent (C) with respect to the molar equivalent number of the acid groups of the (meth) acrylic resin (A)
  • the ratio of the number of molar equivalents of functional groups is taken as an indicator of the degree of crosslinking.
  • both the (meth) acrylic resin (A) and the polyurethane resin (B) have an acid group from the viewpoint of storage stability of the water-based pigment dispersion, adhesion and printing density. It is more preferable that the (meth) acrylic resin (A) and the polyurethane resin (B) be crosslinked by the crosslinking agent (C).
  • a part of each of the acid groups of the (meth) acrylic resin (A) and the polyurethane resin (B) constituting the polymer dispersant is crosslinked by the crosslinking agent (C), and the (meth) acrylic resin (A) interchain
  • a cross-linked structure is formed by crosslinking the polyurethane resin (B) chain and between the (meth) acrylic resin (A) chain and the polyurethane resin (B) chain via a crosslinking agent (C), and polymer dispersion
  • the polymer dispersant is a three or more branched structure represented by the following formula (1) as a crosslinked structure from the viewpoint of storage stability of the water-based pigment dispersion, adhesion and printing density. It is preferable to have
  • X represents a group represented by the following formula (2) or (3), and A represents a group represented by X or an ethyl group.
  • P represents the molecular chain of the (meth) acrylic resin (A) or the molecular chain of the polyurethane resin (B), and * represents the binding site to the quaternary carbon atom in the formula (1)
  • the mass ratio of the pigment in the total solid content of the water-based pigment dispersion [pigment / (total solid content of the water-based pigment dispersion)] is 0 from the viewpoint of storage stability of the water-based pigment dispersion and adhesion and print density.
  • the mass ratio of the pigment to the total amount of the pigment in the water-based pigment dispersion and the (meth) acrylic resin (A) [pigment / [pigment + (meth) acrylic resin (A)]] is the water-based pigment dispersion From the viewpoint of storage stability, adhesion and print density, it is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and preferably 0.95 or less, more preferably Is 0.9 or less, more preferably 0.85 or less.
  • the aqueous pigment dispersion of the present invention comprises a method of dispersing a mixture containing a pigment, a (meth) acrylic resin (A) and a polyurethane resin (B), a pigment, and a (meth) acrylic resin ( After dispersion treatment of either A) or polyurethane resin (B), the other can be further added.
  • the (meth) acrylic resin (A) and the polyurethane resin (B) may each be used as a dispersion in which polymer particles are dispersed in an aqueous medium, and may optionally contain a dispersant such as a surfactant.
  • the dispersion it may be As the dispersion, one synthesized appropriately may be used, or a commercially available product may be used.
  • a commercial item of (meth) acrylic resin (A) for example, "John Krill 390", “John Krill 7100”, “John Krill 734", and "John Krill 538” (all manufactured by BASF Japan Ltd., products)
  • dispersions of vinyl chloride-acrylic resin such as "Binibran 701" (trade name, manufactured by Nisshin Chemical Industry Co., Ltd.).
  • polyurethane resin (B) As a commercial item of the polyurethane resin (B), “NeoRez R-9603” (manufactured by DSM Coating Resins, trade name, aliphatic isocyanate-polycarbonate polyurethane), “Superflex 860” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) A trade name, aromatic isocyanate-polyester polyurethane, etc. may be mentioned.
  • the aqueous pigment dispersion of the present invention is preferably produced efficiently by the method having the following steps 1 and 2 from the viewpoint of storage stability of the aqueous pigment dispersion, adhesion and print density.
  • Step 1 Step of dispersing a pigment mixture containing a pigment, a (meth) acrylic resin (A) having an acid group, and a polyurethane resin (B) to obtain a dispersion
  • Step 2 obtained in Step 1
  • Step 1 The aqueous pigment dispersion of the present invention is preferably produced by a method having the following steps 1-1 and 1-2 before step 1 from the viewpoint of storage stability, adhesion and print density.
  • Step 1-1 Step of dispersing the pigment with the (meth) acrylic resin (A) having an acid group to obtain a preliminary dispersion
  • Step 1-2 Polyurethane resin in the preliminary dispersion obtained in Step 1-1 Adding an emulsion of (B) to obtain a pigment mixture containing a pigment, a (meth) acrylic resin (A) having an acid group, and a polyurethane resin (B)
  • step 1-1 first, the (meth) acrylic resin (A) is dissolved in an organic solvent, and then a pigment, water, and, if necessary, a neutralizing agent, a surfactant, etc. are obtained. Preferred is a method of adding to the solution and mixing to obtain an oil-in-water dispersion.
  • a neutralizing agent a surfactant, etc.
  • the organic solvent for dissolving the (meth) acrylic resin (A) is not particularly limited, but aliphatic alcohols having 1 to 3 carbon atoms, ketones, ethers, esters and the like are preferable, and the wettability to the pigment ( From the viewpoint of improving the solubility of the acrylic resin (A) and the adsorptivity of the (meth) acrylic resin (A), ketones having 4 to 8 carbon atoms are more preferable, and methyl ethyl ketone and methyl isobutyl are more preferable. Ketones are more preferred and methyl ethyl ketone is even more preferred.
  • the solvent used in the polymerization may be used as it is.
  • a part of the acid groups of the (meth) acrylic resin (A) is neutralized using a neutralizing agent from the viewpoint of storage stability of the aqueous pigment dispersion, adhesion, print density and productivity. Is preferred. When neutralizing, it is preferable to neutralize so that pH may be 7 or more and 11 or less.
  • the neutralizing agent include alkali metal hydroxides and ammonia. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide, with sodium hydroxide and potassium hydroxide being preferred.
  • the neutralizing agent is preferably an alkali metal hydroxide from the viewpoint of storage stability of the water-based pigment dispersion, and adhesion and print density.
  • the (meth) acrylic resin (A) may be neutralized in advance.
  • the neutralizing agent is preferably used as an aqueous neutralizing agent solution from the viewpoint of promoting the neutralization sufficiently and uniformly.
  • the concentration of the neutralizing agent aqueous solution is preferably 3% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, from the same viewpoint as above. Preferably it is 25 mass% or less.
  • the use equivalent of the neutralizing agent is preferably 10% by mole or more, more preferably 30% by mole or more, and preferably 80% by mole from the viewpoint of storage stability of the aqueous pigment dispersion, adhesion and print density.
  • the use equivalent of the neutralizing agent can be determined by the following equation.
  • the neutralizer is 100 mol% or less, it is the same as the neutralization, and when the use equivalent of the neutralizer in the following formula exceeds 100 mol%, the neutralizer is (meth) acrylic It means that it is excess with respect to the acid group of resin (A), and the neutralization degree of (meth) acrylic resin (A) at this time is regarded as 100 mol%.
  • the content of each component in the preliminary dispersion is as follows from the viewpoint of storage stability of the water-based pigment dispersion, adhesion, print density, and productivity.
  • the content of the pigment in the predispersion in step 1-1 is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 45% by mass or less. More preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less.
  • the content of the (meth) acrylic resin (A) in the preliminary dispersion in Step 1-1 is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.
  • the content of the organic solvent in the predispersion in step 1-1 is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, and preferably 30% by mass or less More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.
  • the content of water in the preliminary dispersion in Step 1-1 is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 80% by mass or less. More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.
  • the mass ratio of the pigment to the total amount of the pigment in the preliminary dispersion and the (meth) acrylic resin (A) [pigment / [pigment + (meth) acrylic resin (A)]] is the preservation of the aqueous pigment dispersion From the viewpoint of stability, adhesion, print density and productivity, it is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and preferably 0.95 or less. More preferably, it is 0.9 or less, still more preferably 0.85 or less.
  • the dispersion method for obtaining the preliminary dispersion is not particularly limited, and a commonly used mixing and stirring apparatus such as an anchor blade or a disper wing can be used. Among them, a high speed stirring and mixing apparatus is preferable.
  • the temperature of the dispersion treatment in Step 1-1 is preferably 0 ° C. or more, and preferably 40 ° C. or less, more preferably 30 ° C. or less, still more preferably 25 ° C. or less.
  • the dispersion time in Step 1-1 is preferably 0.5 hours or more, and is preferably 30 hours or less, more preferably 10 hours or less, still more preferably 5 hours or less, still more preferably 3 hours or less.
  • step 1-2 an emulsion of polyurethane resin (B) is added to the preliminary dispersion obtained in step 1-1, and a pigment, a (meth) acrylic resin (A) having an acid group, and a polyurethane resin (B) is a step of obtaining a pigment mixture containing
  • the polyurethane resin (B) emulsion is obtained by dispersing polyurethane resin (B) particles in an aqueous medium. It may contain a dispersant such as a surfactant, if necessary.
  • the emulsion of the polyurethane resin (B) improves adhesion to the print medium and also acts as a fixing emulsion for obtaining printed matter with high print density.
  • the content of the polyurethane resin (B) particles in the emulsion of the polyurethane resin (B) is the dispersion stability of the emulsion of the polyurethane resin (B), the storage stability of the aqueous pigment dispersion, and the adhesion, print density and productivity From the point of view, it is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45 It is less than mass%.
  • the content of each component in pigment mixture is as follows from the viewpoint of storage stability of the water-based pigment dispersion, adhesion, print density, and productivity.
  • the content of the pigment in the pigment mixture is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass It is below.
  • the content of the (meth) acrylic resin (A) in the pigment mixture is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, and preferably 20 It is not more than mass%, more preferably not more than 10 mass%, still more preferably not more than 5 mass%.
  • the content of the polyurethane resin (B) in the pigment mixture is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably Is 20% by mass or less, more preferably 15% by mass or less.
  • the content of the organic solvent in the pigment mixture is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass. % Or less, more preferably 15% by mass or less.
  • the content of water in the pigment mixture is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, still more preferably 50% by mass or more, and preferably 85% by mass. % Or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.
  • the mass ratio of the polyurethane resin (B) to the (meth) acrylic resin (A) in the pigment mixture [polyurethane resin (B) / (meth) acrylic resin (A)] is preferably 0.15 or more, more preferably Is 0.5 or more, more preferably 1 or more, still more preferably 1.5 or more, still more preferably 2 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 7 or less More preferably, it is 5 or less.
  • Dispersion treatment of the pigment mixture is preferably performed under control so that shear stress is applied to make the average particle diameter of the pigment particles a desired particle diameter.
  • means for applying shear stress include kneaders such as roll mills and kneaders, high-pressure homogenizers such as Microfluidizer (manufactured by Microfluidic), and media type dispersers such as paint shakers and bead mills.
  • kneaders such as roll mills and kneaders
  • high-pressure homogenizers such as Microfluidizer (manufactured by Microfluidic)
  • media type dispersers such as paint shakers and bead mills.
  • Ultra Apex Mill manufactured by Kotobuki Industry Co., Ltd.
  • Picomill manufactured by Shibata Iron Works Co., Ltd.
  • These devices can also be combined.
  • the pigment can be controlled to have a desired particle diameter by controlling the treatment pressure and the number of passes.
  • the treatment pressure is preferably 60 MPa or more, more preferably 100 MPa or more, still more preferably 150 MPa or more, and preferably 300 MPa or less, more preferably 250 MPa or less, from the viewpoint of productivity and economy.
  • the number of passes is preferably 3 or more, more preferably 7 or more, and preferably 30 or less, more preferably 20 or less.
  • step 1 it is preferable to obtain an aqueous dispersion by further removing the organic solvent from the dispersion by a known method.
  • the organic solvent in the obtained aqueous dispersion is preferably substantially removed, but may remain as long as the object of the present invention is not impaired.
  • the amount of the residual organic solvent is preferably 0.1% by mass or less, more preferably 0.01% by mass or less. Also, if necessary, the dispersion may be heated and stirred before distilling off the organic solvent.
  • Step 2 is a step of crosslinking the dispersion obtained in step 1 using a crosslinking agent (C).
  • a crosslinking agent (C) a crosslinking agent
  • an aqueous pigment dispersion is obtained in which the pigment is dispersed in an aqueous medium with a crosslinked polymer dispersant.
  • some of the acid groups of the (meth) acrylic resin (A) are neutralized in step 1 to disperse the pigment to obtain a dispersion.
  • a water-based pigment dispersion in which a pigment is dispersed in an aqueous medium with a cross-linked polymer dispersant by reacting a part of acid groups possessed by the acrylic resin (A) with a cross-linking agent (C) to form a cross-linked structure. Is preferred.
  • the (meth) acrylic resin (A) and the polyurethane resin (B) have an acid group
  • the (meth) acrylic resin (A) and the polyurethane resin (a) constituting the polymer dispersant Part of each of the acid groups in B) is crosslinked with the crosslinking agent (C)
  • (meth) acrylic resin (A) interchain, polyurethane resin (B) interchain and (meth) acrylic resin (A) chain It is considered that a cross-linked structure is formed by cross-linking between the polyurethane resin (B) and the chain of the polyurethane resin (B) with the cross-linking agent (C).
  • step 2 the dispersion obtained in step 1 and the crosslinking agent (C) are preferably mixed and crosslinked.
  • the amount of the crosslinking agent (C) used in step 2 is the ratio of the molar equivalent number of the crosslinkable functional group of the crosslinking agent (C) to the molar equivalent number of the acid group of the (meth) acrylic resin (A). From the viewpoint of storage stability of the dispersion and adhesion and print density, it is preferably 0.12 or more, more preferably 0.16 or more, still more preferably 0.2 or more, and preferably 0.65 or less. More preferably, it is 0.6 or less, more preferably 0.5 or less, still more preferably 0.4 or less, still more preferably 0.3 or less.
  • the crosslinking time is preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 1.5 hours or more, still more preferably 3 hours or more, from the viewpoint of completion of the crosslinking reaction and economy. And preferably 12 hours or less, more preferably 10 hours or less, still more preferably 8 hours or less, still more preferably 5 hours or less.
  • the temperature of the crosslinking treatment is preferably 40 ° C. or more, more preferably 50 ° C. or more, still more preferably 60 ° C. or more, still more preferably 70 ° C. or more, and preferably 95 ° C. or less from the same viewpoint as described above. And more preferably 90 ° C. or less.
  • the water-based pigment dispersion of the present invention may contain glycerin or triethylene glycol as a moisturizing agent in an amount of 1% by mass or more and 10% by mass or less as a moisturizing agent to prevent drying, and contains additives such as mildewproofing agents May be
  • the additive may be added when dispersing the pigment, or may be added after the dispersion of the pigment or after the crosslinking reaction.
  • the aqueous pigment dispersion of the present invention is preferably such that the pigment-containing polymer particles are dispersed in an aqueous medium containing water as a main medium.
  • the form of the pigment-containing polymer particles is not particularly limited, as long as at least the pigment and the polymer form the particles. That is, particles may be formed of at least a pigment, a (meth) acrylic resin (A) and a polyurethane resin (B).
  • A a (meth) acrylic resin
  • B polyurethane resin
  • a particle form in which a pigment is encapsulated in a polymer a particle form in which a pigment is uniformly dispersed in a polymer, a particle form in which a pigment is exposed on the particle surface of a polymer, and the like are included.
  • the obtained aqueous pigment dispersion may further have a form in which polyurethane resin (B) particles are dispersed in an aqueous medium.
  • the non-volatile component concentration (solid content concentration) of the aqueous pigment dispersion of the present invention is preferably 10% by mass or more, more preferably from the viewpoint of improving the dispersion stability of the dispersion and facilitating the preparation of the aqueous ink. Is 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less.
  • solid content concentration of a water-based pigment dispersion is measured by the method as described in an Example. The average particle diameter of the pigment-containing polymer particles in the water-based pigment dispersion reduces coarse particles, and the storage stability of the water-based pigment dispersion, as well as adhesion and print density are further used as a water-based pigment dispersion for inkjet recording.
  • the water-based ink In order to improve the ejection stability of the water-based ink, it is preferably 50 nm or more, more preferably 60 nm or more, still more preferably 70 nm or more, and preferably 200 nm or less, more preferably 160 nm or less, more preferably 150 nm or less.
  • the average particle diameter of the aqueous pigment dispersion preferably the average particle diameter of the pigment-containing polymer particles, is measured by the method described in the examples.
  • the average particle diameter of the pigment-containing polymer particles in the aqueous ink is the same as the average particle diameter in the aqueous pigment dispersion, and the preferred embodiment of the average particle diameter is the preferred embodiment of the average particle diameter in the aqueous pigment dispersion Is the same as
  • the aqueous pigment dispersion of the present invention is preferably contained in an aqueous ink (hereinafter, also referred to as “aqueous ink” or “ink”) and used.
  • aqueous ink also referred to as “aqueous ink” or “ink”.
  • the aqueous pigment dispersion of the present invention can be used as it is as an aqueous ink, but it is preferable to further contain an organic solvent from the viewpoint of improving the storage stability, adhesion and print density of the aqueous ink.
  • the organic solvent preferably contains one or more organic solvents having a boiling point of 90 ° C. or higher.
  • the weighted average value of the boiling point of the organic solvent is preferably 150 ° C. or more, more preferably 180 ° C. or more, and preferably 240 ° C. or less, more preferably 220 ° C. or less, still more preferably 200 ° C. or less.
  • the organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
  • polyhydric alcohols and polyhydric alcohol alkyl ethers are preferable, and selected from ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, trimethylolpropane and diethylene glycol diethyl ether One or more are more preferable, and propylene glycol is more preferable.
  • the water-based ink may further contain a water dispersion of polymer particles not containing a pigment, from the viewpoint of improving adhesion and printing density.
  • Aqueous dispersions of polymer particles that do not contain pigments can function as fixing aids.
  • the polymer dispersant used in the aqueous pigment dispersion of the present invention is considered to have two different resins adsorbed or fixed to the pigment. Therefore, even when the water-based ink further contains pigment-free polymer particles, the affinity between the polymer particles and the polymer dispersant provides a smooth coating on the print medium, and the pigment particles aggregate locally. Can be suppressed, and the adhesion can be improved without reducing the print density.
  • Polymers that constitute polymer particles containing no pigment include condensation polymers such as polyurethane resin and polyester resin; acrylic resin, styrene resin, styrene-acrylic resin, butadiene resin, styrene-butadiene resin, vinyl chloride Examples include vinyl-based polymers such as base resins, vinyl acetate-based resins and acrylic silicone-based resins.
  • condensation polymers such as polyurethane resin and polyester resin
  • vinyl-based polymers such as base resins, vinyl acetate-based resins and acrylic silicone-based resins.
  • water dispersion of polymer particles containing no pigment those synthesized appropriately may be used, or commercially available products may be used.
  • dispersions of vinyl polymer particles containing no pigment include, for example, “NeoCryl A-1127” (DSM Coating Resins, trade name, anionic self-crosslinking water-based acrylic resin), “Johncryl 390”, Acrylics such as “John Krill 7100”, “John Krill 7600”, “John Krill 537J”, “John Krill PDX-7164", “John Krill 538 J", “John Krill 780” (BASF Japan Ltd., trade name) Resin, urethane resin such as “WBR-2018” “WBR-2000U” (product name from Taisei Fine Chemical Co., Ltd.), “SR-100”, “SR102” (product name from Nippon A & L Co., Ltd.) Styrene-Butadiene resin, "Vinibran 700", “Vinibran 701” (Nisshin Chemical Industries, Ltd.) Company Ltd., vinyl chloride resin, etc.
  • DSM Coating Resins trade name, anionic self-crosslinking water-
  • the content of the aqueous dispersion of pigment-free polymer particles in the aqueous ink is preferably 10% by mass or less, more preferably as a solid content, from the viewpoint of storage stability of the aqueous ink, adhesion and print density. Is 7% by mass or less, more preferably 5% by mass or less.
  • the water-based ink may further contain, if necessary, various kinds of humectants, wetting agents, penetrants, surfactants, viscosity modifiers, antifoams, preservatives, fungicides, rust inhibitors, etc. which are usually used in water-based inks. Additives can be added, and further filtration with a filter or the like can be performed.
  • humectants wetting agents, penetrants, surfactants, viscosity modifiers, antifoams, preservatives, fungicides, rust inhibitors, etc.
  • Additives can be added, and further filtration with a filter or the like can be performed.
  • the contents of the components of the water-based ink and the physical properties of the ink are as follows.
  • the content of the pigment in the aqueous ink is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more from the viewpoint of printing density, and the ink viscosity at the time of solvent volatilization From the viewpoint of lowering the storage stability and improving storage stability, it is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less.
  • the total content of the pigment and the polymer dispersant in the water-based ink is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 7% from the viewpoint of adhesion.
  • the content is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 12% by mass or less, from the viewpoint of reducing the ink viscosity at solvent volatilization and improving storage stability. is there.
  • the content of the organic solvent in the water-based ink is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more from the viewpoint of storage stability of the water-based ink and adhesion and printing density. And preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
  • Water content The content of water in the water-based ink is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more from the viewpoint of storage stability of the water-based ink and adhesion and printing density. And preferably 90% by mass or less, more preferably 85% by mass or less.
  • the mass ratio of the pigment in the total solid content of the water-based ink is preferably 0.25 or more, from the viewpoint of storage stability of the water-based ink and adhesion and print density. More preferably 0.3 or more, still more preferably 0.35 or more, still more preferably 0.4 or more, and preferably 0.75 or less, more preferably 0.7 or less, more preferably 0.6 The following is more preferably 0.5 or less.
  • the viscosity of the aqueous ink at 32 ° C. is preferably 2 mPa ⁇ s or more, more preferably 3 mPa ⁇ s or more, still more preferably 5 mPa ⁇ s or more, and preferably 12 mPa ⁇ s or less from the viewpoint of storage stability. More preferably, it is 9 mPa ⁇ s or less, more preferably 7 mPa ⁇ s or less.
  • the viscosity of the water-based ink can be measured using an E-type viscometer.
  • the pH of the water-based ink at 20 ° C. can be measured by a conventional method.
  • the water-based ink can be suitably used for flexographic printing ink, gravure printing ink, or inkjet ink, and is particularly preferably used for inkjet ink. It can be loaded into a known ink jet recording apparatus and discharged as ink droplets on a print medium to record an image or the like.
  • an inkjet recording apparatus there are a thermal type and a piezo type, and it is more preferable to use a water based ink containing the water based pigment dispersion of the present invention as a piezoelectric type water based ink for inkjet recording.
  • print media that can be used include highly absorbent normal paper, low absorbent coated paper, and non-absorbent resin film.
  • the resin film is preferably at least one selected from polyester films, polyvinyl chloride films, polypropylene films, and polyethylene films.
  • the resin film may use a corona-treated substrate.
  • Lumirror T60 made by Toray Industries, Inc., polyester
  • PVC80BP made by Lintec Co., Ltd., vinyl chloride
  • DGS-210WH made by Rowland DG Corporation, vinyl chloride
  • transparent PVC RE-137 made by Mimaki Engineering, vinyl chloride
  • Kainas KEE70CA made by Lintec Co., Ltd., polyethylene
  • Yupo SG90 PAT1 made by Lintec Co., Ltd., polypropylene
  • FOR, FOA all made by Futamura Chemical Co., Ltd.
  • Bonille RX made by Kojin Film & Chemicals Co., Ltd., nylon
  • Emblem ONBC made by Unitika Co., Ltd., nylon
  • the remaining 90% of the monomer mixture, 0.27 parts of the polymerization chain transfer agent, 60 parts of MEK, and an azo-based radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) in a dropping funnel.
  • the mixture in the funnel was dropped over 3 hours.
  • Preparation Example 2 30 parts of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., reagent), 100 parts of styrene (manufactured by Wako Pure Chemical Industries, Ltd., reagent), styrene macromer (manufactured by Toagosei Co., Ltd., trade name: AS-6S, number average molecular weight 60 parts (30 parts as solid content), polypropylene glycol monomethacrylate (manufactured by NOF Corporation, trade name: Blenmer PP-800, average addition mole number of propylene oxide 13, end: hydroxyl group) 40 parts were mixed to prepare a monomer mixture.
  • methacrylic acid manufactured by Wako Pure Chemical Industries, Ltd., reagent
  • styrene macromer manufactured by Toagosei Co., Ltd., trade name: AS-6S, number average molecular weight 60 parts (30 parts as solid content
  • polypropylene glycol monomethacrylate
  • Example 1 35 parts of the (meth) acrylic resin (A-1) obtained by drying the polymer solution obtained in Preparation Example 1 under reduced pressure is mixed with 40 parts of MEK, and 5N aqueous sodium hydroxide solution (sodium hydroxide solid content 16) .9%, Wako Pure Chemical Industries, Ltd., 14 parts of volumetric titration was added, and the (meth) acrylic resin (A-1) was neutralized so that the usage equivalent of the neutralizing agent was 40 mol% .
  • Step 1-2 A polyurethane resin (B-1) emulsion (aliphatic isocyanate-polycarbonate polyurethane emulsion, trade name “NeoRez R-9603”, manufactured by DSM Coating Resins, Inc., with respect to the preliminary dispersion (1) obtained in step 1-1, A pigment mixture was obtained by adding a solid content of 38%, an acid value of 32 mg KOH / g, 504 parts (active solid content 191.5 parts), 60 parts of MEK, and 650 parts of ion exchanged water (W1).
  • B-1 emulsion aliphatic isocyanate-polycarbonate polyurethane emulsion, trade name “NeoRez R-9603”, manufactured by DSM Coating Resins, Inc.
  • Step 1 The pigment mixture obtained in step 1-2 was subjected to 10-pass dispersion treatment with a microfluidizer (manufactured by Microfluidics, trade name) at a pressure of 200 MPa to obtain a dispersion. After adding 260 parts of ion-exchanged water (W2) to the obtained dispersion and stirring, MEK is removed at 60 ° C.
  • a microfluidizer manufactured by Microfluidics, trade name
  • a filter with a pore diameter of 5 ⁇ m acetyl cellulose membrane, A dispersion with a solid content concentration of 25% by filtering with a 25 mL needleless syringe (manufactured by Terumo Corporation) with an outer diameter of 2.5 cm and manufactured by Fujifilm Corporation and removing coarse particles I got d-1).
  • Step 2 100 parts of the dispersion (d-1) obtained in step 1 is taken in a glass bottle with a screw cap, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name "Denacol EX-321L” as a crosslinking agent (C) , 0.35 parts of epoxy equivalent weight was added, sealed up, and heated at 70 ° C. for 5 hours while stirring with a stirrer.
  • trimethylolpropane polyglycidyl ether manufactured by Nagase ChemteX Co., Ltd., trade name "Denacol EX-321L” as a crosslinking agent (C) , 0.35 parts of epoxy equivalent weight was added, sealed up, and heated at 70 ° C. for 5 hours while stirring with a stirrer.
  • the temperature is lowered to room temperature, and filtration is performed with a 25 mL needleless syringe (manufactured by Terumo Corporation) having a pore diameter of 5 ⁇ m filter (acetyl cellulose membrane, outer diameter: 2.5 cm, manufactured by Fujifilm Corporation) attached.
  • An aqueous pigment dispersion (D-1) having a concentration of 25% was obtained.
  • the average particle size was 102 nm.
  • Example 2 286 parts (108.7 parts of effective solid content) of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1, 50 parts of MEK, and 480 parts of ion exchanged water (W1); An aqueous pigment dispersion (D-2) was obtained in the same manner as in Example 1, except that the amount of Denacol EX-321L added was changed to 0.47 parts.
  • Example 3 153 parts of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1 (active solids 58.1 parts), 40 parts of MEK, 380 parts of ion exchanged water (W1), ion exchange in step 1
  • a water-based pigment dispersion (D-3) was prepared in the same manner as in Example 1, except that water (W2) was changed to 160 parts, and the amount of Denacol EX-321L added in step 2 was changed to 0.59 parts. Obtained.
  • Example 4 25 parts of (meth) acrylic resin (A-1), 35 parts of MEK, 10 parts of 5N aqueous sodium hydroxide solution, and 164 parts of ion-exchanged water in step 1-1 of Example 1; 97 parts of polyurethane resin (B-1) emulsion in (2) (36.9 parts of effective solid content), 30 parts of MEK, 320 parts of ion exchanged water (W1), 140 parts of ion exchanged water (W2) in step 1
  • a water-based pigment dispersion (D-4) was obtained in the same manner as in Example 1, except that the amount of Denacol EX-321L added in step 2 was changed to 0.5 parts.
  • Example 5 25 parts of (meth) acrylic resin (A-1), 35 parts of MEK, 10 parts of 5N aqueous sodium hydroxide solution, and 164 parts of ion-exchanged water in step 1-1 of Example 1;
  • the amount of Denacol EX-321L in step 2 is changed by changing 35 parts of polyurethane resin (B-1) emulsion in Example 2 (13.3 parts of effective solid content), 30 parts of MEK, and 270 parts of ion exchanged water (W1).
  • An aqueous pigment dispersion (D-5) was obtained in the same manner as in Example 1, except that the addition amount was changed to 0.6 parts.
  • Example 6 (Meth) acrylic resin (A-2) obtained by drying under reduced pressure the polymer solution obtained in Preparation Example 2 of the (meth) acrylic resin (A-1) in step 1-1 of Example 1 , MEK changed to 37 parts, 5N aqueous sodium hydroxide solution changed to 5.86 parts, polyurethane resin (B-1) emulsion in step 1-2 291 parts (active solids 110.6 parts), MEK Aqueous pigment dispersion in the same manner as in Example 1 except that 50 parts of water, W1 ion exchange water was changed to 480 parts, and the addition amount of Denacol EX-321L in step 2 was changed to 0.195 parts Obtained (D-6).
  • Example 7 (Meth) acrylic resin (A-2) obtained by drying under reduced pressure the polymer solution obtained in Preparation Example 2 of the (meth) acrylic resin (A-1) in step 1-1 of Example 1 80 parts of MEK, 6 parts of 5N aqueous solution of sodium hydroxide and 140 parts of ion exchanged water, and the polyurethane resin (B-1) emulsion in step 1-2 is a polyurethane resin (B-2) emulsion (Aromatic isocyanate-polyester polyurethane emulsion, trade name "Superflex 860", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content 35%) 315 parts (active solid content 110.3 parts), 30 parts MEK, ion exchange Change 460 parts of water (W1) to 190 parts of ion-exchanged water (W2) in step 1, and add 0,0 parts of Denacol EX-321L in step 2. Except for changing the part to obtain an aqueous pigment dispersion (D-7)
  • Example 8 286 parts (108.7 parts of effective solid content) of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1, 50 parts of MEK, and 480 parts of ion exchanged water (W1); Example 1 except that Denacol EX-321L in Example 1 was changed to 0.55 parts of 1,6-hexanediol diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name “Denacol EX-212”, epoxy equivalent weight 151). An aqueous pigment dispersion (D-8) was obtained in the same manner as in the above.
  • Example 9 286 parts (108.7 parts of effective solid content) of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1, 50 parts of MEK, and 480 parts of ion exchanged water (W1); An aqueous pigment dispersion (D-9) was obtained in the same manner as in Example 1, except that the addition amount of Denacol EX-321L in was changed to 0.29 parts.
  • Example 10 286 parts (108.7 parts of effective solid content) of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1, 50 parts of MEK, and 480 parts of ion exchanged water (W1); An aqueous pigment dispersion (D-10) was obtained in the same manner as in Example 1, except that the amount of Denacol EX-321L added was changed to 0.7 parts.
  • Example 11 286 parts (108.7 parts of effective solid content) of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1, 50 parts of MEK, and 480 parts of ion exchanged water (W1); An aqueous pigment dispersion (D-11) was obtained in the same manner as in Example 1, except that the addition amount of Denacol EX-321L in was changed to 0.98 parts.
  • Comparative Example 1 Change 18 parts of (meth) acrylic resin (A-1), 30 parts of MEK, 7 parts of 5N aqueous solution of sodium hydroxide, and 160 parts of ion-exchanged water in Step 1-1 of Example 1 to Step 1 10 parts of polyurethane resin (B-1) emulsion at -2 (3.8 parts of effective solid content), 20 parts of MEK, 240 parts of ion exchanged water (W1), 100 parts of ion exchanged water (W2) in step 1 A water-based pigment dispersion (D-C1) was obtained in the same manner as in Example 1 except that the amount of Denacol EX-321L added in step 2 was changed to 0.5 parts.
  • Comparative example 2 286 parts (108.7 parts of effective solid content) of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1, 50 parts of MEK, and 480 parts of ion exchanged water (W1); An aqueous pigment dispersion (D-C2) was obtained in the same manner as in Example 1, except that the amount of Denacol EX-321L added was changed to 0.16 parts.
  • Comparative example 3 286 parts (108.7 parts of effective solid content) of the polyurethane resin (B-1) emulsion in step 1-2 of Example 1, 50 parts of MEK, and 480 parts of ion exchanged water (W1); An aqueous pigment dispersion (D-C3) was obtained in the same manner as in Example 1, except that the amount of Denacol EX-321L added in the above was changed to 1.37 parts.
  • Comparative example 4 132.4 parts of (meth) acrylic resin (A-1) obtained by drying under reduced pressure the polymer solution obtained in Preparation Example 1 is mixed with 51 parts of MEK, and 5N aqueous sodium hydroxide solution (sodium hydroxide solid 16.9%, Wako Pure Chemical Industries, Ltd., 52.2 parts for volumetric titration was added, and the neutralization agent was neutralized so that the working equivalent of the neutralizing agent was 40% (degree of neutralization 40%).
  • Step 1'-2 160 parts of ion exchanged water (W1) was added to the preliminary dispersion (4 ′) obtained in Step 1′-1 to obtain a pigment mixture.
  • Step 1 ' The pigment mixture obtained in Step 1′-2 was subjected to 10-pass dispersion treatment with a microfluidizer (manufactured by Microfluidics, trade name) at a pressure of 200 MPa to obtain a dispersion. After 180 parts of ion exchanged water (W2) is added to the obtained dispersion and stirred, MEK is removed at 60 ° C.
  • a microfluidizer manufactured by Microfluidics, trade name
  • a filter with a pore diameter of 5 ⁇ m acetyl cellulose membrane, A dispersion with a solid content concentration of 25% by filtering with a 25 mL needleless syringe (manufactured by Terumo Corporation) with an outer diameter of 2.5 cm and manufactured by Fujifilm Corporation and removing coarse particles d-C4) was obtained.
  • Step 2 ' 100 parts of the dispersion (d-C4) obtained in step 1 'is put into a screw-capped glass bottle, and trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name "Denacol EX-" as a crosslinking agent (C) Add 321 L ′ ′, epoxy equivalent weight 129) 1.62 parts, close tightly, and heat at 70 ° C. for 5 hours while stirring with a stirrer.
  • Comparative example 5 38 parts of (meth) acrylic resin (A-1), 30 parts of MEK, 15 parts of 5N aqueous solution of sodium hydroxide, and 285 parts of ion exchanged water in step 1'-1 of Comparative Example 4
  • An aqueous pigment dispersion (D-C5) was obtained in the same manner as in Comparative Example 4, except that Denacol EX-321L in 2 'was changed to 0.78 parts.
  • Example 12 and 13 and Comparative Example 6 a polyurethane resin emulsion (trade name "NeoRez R-9603" is used as an aqueous dispersion of polymer particles containing no pigment at the time of ink preparation, using the aqueous pigment dispersion shown in Table 3. , DSM Coating Resins) was added. The following tests 2 and 3 were performed and evaluated using the obtained water-based inks 1 to 13 and C1 to C6. The results are shown in Tables 1 to 3. The composition of the ink shown in Tables 1 to 3 indicates the blending amount (%) of each component when the total amount of the ink is 100%. Further, each notation in Tables 1 to 3 is as follows.
  • Test 2 Evaluation of print density
  • bar coater No. It applied to polyester film (Toray Industries, Inc. make, trade name “Lumirror T60", 75 micrometers in thickness) using 4 (made by As One), and heated at 60 degreeC for 10 minutes.
  • a Macbeth densitometer manufactured by Gretag Macbeth, product number: Spectroeye
  • a total of five points of the center and four corners of the obtained printed matter (5.1 cm ⁇ 8.0 cm) are measured And the average value was obtained. The larger the value, the better the print density.
  • Test 3 Evaluation of adhesion
  • a cellophane tape (Nichiban tape width 18 mm ⁇ 4 cm) is attached to the coating film of the printed matter obtained in the evaluation of the printing density, and after standing for 1 minute, the tape is vertically oriented to the coating film.
  • the peeling area of the coating film was visually confirmed from the state of the coating film after pulling and peeling, the thing which all the coating film whole surfaces peeled was made into 100% of peeling area, and it evaluated based on the following evaluation criteria. It is excellent in adhesiveness as it is 2 or more by the following evaluation criteria.
  • the polymer dispersant contains (meth) acrylic resin (A) and polyurethane resin (B), and the degree of crosslinking is 0.12 or more. Since the mass ratio [pigment / (total solid content of the water-based pigment dispersion)] is not more than 65 and not more than 65, the storage stability is excellent, and excellent adhesion and high print density can be achieved. You can see that On the other hand, Comparative Example 1 has a mass ratio [pigment / (total solid content of water-based pigment dispersion)] of 0.8, so storage stability, adhesion and print density are inferior to Examples 1 to 13. .
  • Comparative Example 2 has a degree of crosslinking of 0.08, so storage stability and print density are poor.
  • Comparative Example 3 has a degree of crosslinking of 0.70, so storage stability, adhesion and print density are inferior.
  • Comparative Example 4 since the polyurethane resin (B) is not contained as a polymer dispersant, adhesion is poor despite the large amount of resin in the system, and it is useful that the polymer dispersant contains a polyurethane resin (B). I understand that there is.
  • Comparative Example 5 does not contain the polyurethane resin (B) as the polymer dispersant, so that the mass ratio [pigment / (total solid content of the water-based pigment dispersion)] in the crosslinking degree range of 0.12 or more and 0.65 or less Even in the range of 0.25 or more and 0.75 or less, the adhesion is poor.
  • Comparative Example 6 does not contain a polyurethane resin (B) as a polymer dispersant, and a polyurethane resin emulsion is added at the time of preparation of the ink. However, although there is adhesion, the printing density is low, and adhesion and printing density It can be seen that the coexistence of both has not been achieved.
  • an aqueous pigment dispersion having a high printing density while maintaining excellent adhesion to a non-water absorbing print medium by using the aqueous ink excellent in storage stability the aqueous pigment dispersion It is possible to provide an aqueous ink containing the same and a method for producing the aqueous pigment dispersion.

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Abstract

L'invention concerne une dispersion aqueuse de pigment dans laquelle un pigment a été dispersé dans un milieu aqueux au moyen d'un agent dispersant polymère. L'agent de dispersion contient une résine (méth)acrylique (A) contenant un groupe acide et une résine de polyuréthane (B). La résine (A) est réticulée par un agent de réticulation (C) et le degré de réticulation de la résine (A) est de 0,12 à 0,65. La dispersion aqueuse de pigment présente un rapport massique pigmentaire [pigment/(teneur totale en solides de la dispersion aqueuse de pigment] de 0,25 à 0,75. L'invention concerne également un procédé de production d'une dispersion aqueuse de pigment, le procédé de production présentant une étape 1 dans laquelle une dispersion est obtenue par réalisation d'un traitement de dispersion sur un mélange pigmentaire qui comprend un pigment, une résine (méth)acrylique (A) contenant un groupe acide et une résine de polyuréthane (B) et une étape 2 dans laquelle la dispersion obtenue à l'étape 1 est réticulée à l'aide d'un agent de réticulation (C).
PCT/JP2018/048535 2017-12-28 2018-12-28 Dispersion aqueuse de pigment WO2019132023A1 (fr)

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CN111511850A (zh) 2020-08-07
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EP3733795A4 (fr) 2021-12-01
JP7184514B2 (ja) 2022-12-06

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